2-aryl-4, 5-arylo-1, 2, 3-triazole



United States Patent 3,189,615 2-ARYL-4,5-ARYLO-1,2,3-TRIAZOLE Hansjorg Heller, Basel, Ernst Keller, Basel-Land, and

Hermann Gysling, Basel, Switzerland, and Fritz Mindermann, Baden, Germany, assignors to J. R. Geigy, A.-G., Basel, Switzerland, a Swiss firm No Drawing. Original application Dec. 10, 1957, Ser. No. 701,719, now Patent No. 3,004,896, dated Oct. 17, 1961. Divided and this application Oct. 3, 1961, Ser. No. 142,537

Claims priority, application Switzerland, Dec. 14, 1956,

40,67 4/ 5 6 8 Claims. (Cl. 260-308) are elfective non-actinic agents. In this formula the triazole ring is written in the conventional manner but the arrangement of the valences at the nitrogen atom is left undetermined. In this formula: A represents a phenylene radical bound by two neighbouring carbon atoms to two nitrogen atoms of the triazole ring, and B represents a phenyl radical having a free hydroxyl group in the 2-position with regard to the linkage with the triazole ring and 'ice halogen benzyl groups; aryl groups such as phenyl or alkoxyphenyl groups; R-O-groups wherein R represents hydrogen, an alkyl radical, aralkyl radical such as benzyl, an aryl radical such as phenyl, chlorophenyl or alkylphenyl radical; carbacyl groups such as an alkyl carbonyl, arylcarbonyl or alkoxycarbonyl radical; R-CO-groups wherein R represents hydrogen, an alkyl radical, an aralkyl radical such as benzyl, an aryl radical such as phenyl or chlorophenyl radical; a hydroxyl group, an alkoxy or an aryloxy group, an amino radical, an organically substituted amino radical, e.g., a monoalkyl, monocycloalkyl, monoaralkyl or monophenylamino group, a dialkylamino group, dicycloalkylamino group, diaralkylamino group, alkylaralkylamino group or alkylphenylamino group; R-SOzgroups in which a R represents a hydroxyl group, an alkyl radical, aralkyl radical such as benzyl, aryl radical such as phenyl, alkyl phenyl or alkoxy phenyl radical, an amino group such as H N-, an organically substituted amino group such as, e.g., a monoalkyl, monocycloalkyl, monoaralkyl, monophenyl, dialkylamino group, diaralkyl amino groups such as dibenzyl amino group, dicycloalkyl amino groups such as dicyclohexylamino group, alkylaralkyl amino groups such as alkylbenzyl amino groups and an alkylaryl amino group such as alkylphenyl amino groups, can be used as substituents of the aromatic rings, in particular of the radicals which can be further substituted in other positions, in

particular by lower alkyl, lower alkoxy, lower carbalkoxy, cyclohexyl, phenyl groups and halogen. Compounds containing such substituents in the 5-position are advantageous.

Particularly valuable subclasses of non-actinic agents according to the present invention (actively UV-absorbing compounds) are compounds having a free hydroxyl' group in the 2-position with regard to the linkage with the triazole ring and which are substituted in the 3- and 5- or in the 4- and S-positions by lower alkyl and chlorine.

In order to attain the absorption necessary for cosmetic purposes (absorption of UV rays up to 320 m causing erythema but non-absorption of sun-tanning rays about 350 mp it is particularly advantageous if B represents a phenyl radical having in the o-position a substituent R (R being an alkyl, aralkyl, aryl, acyloxy, alkoxy or aralkoxy radical, preferably lower alkyl, lower alkoxy and acyloxy radicals). This phenyl radical can also be substituted in further positions as defined, in particular by hydrocarbon radicals such as, e.g., lower alkyl, hydroxyl groups or halogen.

In particular compounds which contain a lower alkoxy ,or acyloxy or a lower alkyl group in the 2-position with groups such as methyl, ethyl, butyl, amyl, octyl, dodecyl I A and B.

All these groups are bound to the rings A and B by carbon, oxygen or sulphur atoms. If aromatic radicals are substituents or are in substituents, they can be substituted as A or B. Aromatic radicals should be bound to A or B either direct as in diphenyl derivatives or by means of saturated divalent bridging members not having dyeing characteristics. Examples of such bridging members are saturated hydrocarbon radicals, oxygen or sulphur ether atoms, carbonyl, ,sulphoxide, sulphonyl, disulphimide, carboxyl-sulphimide groups.

The compounds according to the present invention are produced by coupling aryldiazonium compounds with azo components of the benzene and naphthalene series coupling in the o-position to a primary amino group, which azo components may also be further substituted as defined, and oxidising the o-aminoazo dyestutfs thus formed to the corresponding 1.2.3-triazole compound. They can also be produced by coupling o-nitro aryl diazonium compounds of the benzene or naphthalene series with phenols or naphthols coupling in the oor p-positions or with amines of the benzene and naphthalene series cou pling in the p-positions to a primaryvamino group, and then reducing the o-nitro-azo dyestutis by the usual methods, e.g., with ammonium sulphide or with zinc in an alkaline medium to form the 1.2.3-triazole compounds. In these processes also the aromatic rings can be further substituted as defined. In the end product free hydroxyl groups can also be alkylated or acylated. Primary amino groups must be removed by diazotising them and replacing the diazo group, by the usual methods, by for example, hydrogen, halogen or cyano or hydroxyl groups.

The triazole compounds according to the present invention are incorporated into the material to be protected from UV rays or into the protective foils and coverings in amounts varying from fractions of percentages to several percent. The protected material or protective coverings can contain, for example 0.001% to 15% of the active ingredient and should contain, advantageously 0.01% to 5.0%. In non-actinic agents for the human skin, the content of active ingredient should be advantageously 01-10% calculated on the non-volatile components of the preparation.

It is known that of substances suggested as non-aotinic agents in the literature, only the o-hydroxybenzophenones have been used to a certain extent in technics because Patented June 15, 1965 3 their properties more or less meet the very high requirements. In the same technical application, the triazole compounds used according to the present invention have the following advantages over the known products: hav- 4 The reason for the activity of the triazole compounds claimed according to the present invention probably lies in their capability to absorb ultra-violet light, as can be seen from the following: i

ing similar fastness to light, their absorption of the ultra- 5 The ultra-violet transmission is determined with light violet light is much stronger or, having similar absorpof 350-380 m This transmission is measured in pertion of UV-light, they are much more fast to light. cent in the following Table 1(b):

By a suitable choice of substituents, compounds can also be found amongst the non-actinic agents accord- Table ing to the present invention which can be used as skinprotecting agents. They prevent erythema occurring but Percent transmission in do not prevent tanning. light ot350-380 mu The favourable efiects according to the present inven- Nmmtmm agent tion are astonishing in view of the fact that the fastness Unexposed Alter 1,000 h. to light of the [4. 5-arylo1.2.3-triazinyl] compounds of the stil-bene and p-phenylene series which have a strong I 2-(2'-hydrpxy-5'-methylphenyl)- About1. About 1. fluorescence in daylight and up to now have been used nu" aff g g Do. as optical brightening agents in the textile industry 18 one gei zt tri olescarbox lic acid order of magnitude lower. These compounds are there- In a lf f 5mm) d D fore less suitable as non-actinic agents for technical pur- 20 phe yDg-c hlbroben tfiazolo. m o poses IV... 2-%-hydt:igg-5-amylphenyl)- Do.

e o e.

In this description the expressions non-actimc comv.. 2-(2'-hydroxy-5-tert.butyl --do.--.-- Do. pounds and UV-absorbing compounds are regarded as ggf ggig ggg gfa 23 equivalent. benzophenone).

The following examples illustrate the present inven- 25 31mm 97 tion. Parts are given as parts by weight and the temperaare degrees centlgrade' Table 1(b) shows that the triazole compounds used ac- EXAMPLE 1 cording to the present invention more completely absorb the ultra-violet rays also after longer exposure than Res- Cellulose acetate foils are produced by dissolving 15.0 32 2 55282: z ifi figg zg g i l m techmcs parts of acetyl cellulose (2.5 of the 3 OH groups per y y g glucose unit esterified with acetic acid), 0.3 part of one EXAMPLE 2 of the non-actinic agents given in the following Tables 1(a) and 1(b) and 2.0 parts of dibutyl phthalate in 35 Foils are produced asinExample 1 but instead of acetyl Parts Of 366M116 and drawing a fi from t $0111- cellulose, a cellulose ester containing 0.5 benzoyl groups tion on to glass. The foils which are first dried at room and 2.1 acetyl groups per glucose unit is used. temperature and then in theoven at 60 are 0.04 mm. The foils were tested for folding and transmission of thick. Samples thereof are exposed to light for 1000 UV light and the results given in the following table were hours in the fade-o-meter and then tested for brittleness obtained:

' Table 2 Behaviour of film on folding Percent transmission with light 01350-380 m No. Non-actinle agent Before After 1,000 h. Before After 1,000 h. exposure exposure QXPOSlll-B BXPOSUI'B I 2-(2-hydroxy-3'.5-dlmethyl phenyl)- Unchanged..- Unchanged-- Aboutl About 1. benzotriazole. II- 2-(2-hydroxy-3'.5-dlmethyl-phenyl)- do (in 5-methoxy-benzotriazole. III- 2-(2-hydroxy-3'.5-dimethyl-pheny1)- do (in in emethyl-benzotriazole. IV 2-(2'-hydroxy-5'-carbethoxy-phenyl)- do 35 39.

benzotriazole. 0 Blind feet (in Snlit 98 97,

by folding. The results are summarised in the following table:

The table shows that the UV part of the light is absorbed practically unchanged by the triazole compounds used according to the present invention, also after longer exposure.

EXAMPLE 3 The usual marketed polyester (IQ-312, Standard Polyester of the Interchemical Corporation, New York), such as is used for the production of polyester resin plates and which does not contain a light stabiliser is polymerised, after incorporation of 0.1% of the non-actinic agents according to the present invention given below, the polymerisation being performed at a raised temperature with the help of 1% of benzoyl peroxide, into 4 mm. thick, optically clear plates. Samples of the plates are exposed for 1000 hours in the fade-o-meter, after which time the light transmittancy is determined. Table 3 shows the results obtained:

Instead of the compounds given in Table 3, also the following substances can be used with similar results. They are distinguished by the wave length of the absorption maximum having the longest wave length. The spectrum is taken in methyl alcohol:

, (1) 2-(2 hydroxy-S' methoxy-phenyl) benzotriazole V 350 (2) 2-(2-hydroxy-5-methyl-phenyl-)5.6 dichlorobenzotriazole 342 (3) 2-(2'-hydroxy-5phenyl-phenyl) chlorobenzotriazole 342 (4) 2-(2-hydroxy 5- c yclohexyl-phenyl 5 chlorobenzotriazole 341 (5) 2-(2'-hydroxy-5-eyclohexyl phenyl) benzotriazole 338 (6) 2-(2'-hydroxy-4.5'-dimethyl-pheny1) benzotriazole-5-carboxylic acid butyl ester 347 (7) 2-(2-hydroxy-3'.'5' dichlorophenyl) benzotriazole 335 (8) 2-(2'-hydroxy-4.5 dichlorophenyl) benzotriazole 334 (9) 2-(2' hydroxy 5' methyl-phenyl) benzotriazole-S-ethylsulphone 350 (10) 2-(2-hydroxy-3'.5' dimethyl-phenyl) benzo triazole-S-ethylsulphone 351 (ll) 2-(2'-hydroxy 5 phenyl phenyl) benzotriazole 340 (12) 2-(2-hydroxy-5-methoxy-phenyl) 5 methylbenzotriazole 350 EXAMPLE 4 Foils from a mixture consisting of:

66 parts of polyvinyl chloride pulverised, 33 parts of dioctyl phthalate, 1 part of non-actinic agent are produced on a roller frame at 150. Samples of these foils are exposed for 720 hours in the fade-o-meter. The results given in Table 4 are obtained:

EXAMPLE 5 A non-actinic preparation for the human skin which prevents erythema but allows tanning is obtained as follows:

5 parts of white ceresin wax,

22 parts of white petrolatum,

19.5 parts of white mineral oil,

15 parts of lanolin, anhydrous,

2 parts of a compound named in Table 5, 36 parts of water and,

0.5 part of perfume.

The non-actinic preparation is produced by first melting the ceresin, petrolatum and the lanolin together and dispersing one of the benzotriazole derivatives mentioned in the following Table 5 in the melt. Mineral oil is then added at and water is then slowly introduced at the same temperature. Stirring is continued until the temperature has dropped at 50 whereupon the perfume is added. I

The amounts of 0.1 to 7 parts of non-actinic agent can be used in the composition depending entirely on the intended use, for example at high altitudes, on the beach etc.

A non-actinic preparation for the human skin which can be sprayed is obtained if 10 parts of ricinoleic acid methyl ester, 10 parts of oleyl alcohol and 1 part of 2- (2'.6-dirnethy1-4'-hydroxyphenyl)-benzotriazole are dissolved in 80 parts of ethanol. After the addition of the usual marketed Freon propellants, the solution can be sprayed from an aerosol. It protects the skin from erythema without preventing tanning by the sun.

What is claimed is:

1. An ultraviolet light-absorbing compound, capable of protecting materials sensitive to ultraviolet light, of the formula wherein A is an o-phenylene group bound by two neighbouring carbon atoms to two nitrogen atoms of the triazole ring, said o-phenylene group being selected from the group consisting of unsubstituted o-phenylene, o-phenylene carboxylic acid(lower)alky1 ester, ethyl sulphonyl-ophenylene, chloro-o-phenylene, lower alkoxy-o-phenylone, and lower alkyl-o-phenylene, and B is Z-hydroxyphenyl substituted by a member selected from the group consisting of lower alkyl, lower alkoxy, lower carbalkoxy,

70 cyclohexyl, phenyl and chlorine.

7 6. 2 (2'-hydroxy-5'-tert. butyl-phenyl) 5 chloro- References Cited by the Examiner UNITED STATES PATENTS Zitscher 260-308 Conzetti et a1. 260-308 Brunner et a1. 260-308 Keller et a1. 260-308 Anderson 260-308 Boyle et a1. 260-308 Milionis et a1. 260-308 Dickson 260-308 8 OTHER REFERENCES Beilsteins Handbuch der OrganischenChemie, vol. 26

(Berlin, 1954), Second Supplement, pages Benson et 3.1., Chemical Reviews, vol.

46, page 39 Chakrabarty, Chermcal Abstracts, vol. 23, page 836 0 Itomi, Chem. Abstracts, Vol. 24, pages 2060-1 (1930).

Karrer, Organic Chemistry (NewYork, 1946), page MODANCE, Examiners.

Disclaimer 3,189,615.Hamj0rg Heller, Basel, Ernst Keller, Basel-Land, and Hemcm'n Gysling, Basel, Switzerland, and Fritz Mindermann, Baden, Germany. 2-ARYL-4,5-ARYLO-1,2,3-TRIAZOLE. Patent dated June 15, 1966?. Disclaimer filed Dec. 3, 1975, by the assignee, H. A. Whitten c@ 0. Hereby enters this disclaimer to claims 1 through 8, inclusive, of said patent.

[Ofiicz'al Gazette March 16, 1976.] 

1. AN ULTRAVIOLET LIGHT-ABSORBING COMPOUND, CAPABLE OF PROTECTING MATERIALS SENSITIVE TO ULTRAVIOLET LIGHT, OF THE FORMULA 